I completely missed that you were using xfce. I apologize. I checked the 
default settings for gnome and it does not have those presets. (I have included 
a picture)
The command should be "totem /media/cdrom0" unless you have multiple drives. 
Also, the command "totem /dev/dvd" will work. 

On a side note, if you want to skip the title screens and go straight
into a movie, (I am not sure how to with totem...) you can use vlc to
select the track. "vlc /dev/d...@1" where one is the track (all the
movies I have tried have started at 1)

hope this helps

** Attachment added: "Screenshot-File Management Preferences.png"
   
http://launchpadlibrarian.net/24296058/Screenshot-File%20Management%20Preferences.png

-- 
Totem won't autoplay DVD
https://bugs.launchpad.net/bugs/347045
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